Light-sensitive silver halide photographic material

ABSTRACT

A new polymer compound having the guanidyketimine structural unit of the formula WHEREIN X is an acid radical and n is 1 or 2 has been synthesized. The said compound is useful as a mordant in a lightsensitive silver halide photographic material in order to prevent undesired migration of an acidic dye contained in a certain layer of the said photographic material. This greatly enhances sharpness to the image obtained from the said photographic material.

United States Patent 1151 3,706,563 Ushiyama et al. 14 1 Dec. 19, 1972 '154] LIGHT-SENSITIVE SILVER HALIDE 3,625,691 12/1971 Ohyama et al ..96/84 A PHOTOGRAPHIC MATERIAL Primary Examiner-Ronald H. Smith [72] Inventors: R1ntaro Ushlyama, Hach1o 1-sh1,

Tokyo; Osaka sugino, Machida Attorney-Waters, Rod1t1, Schwartz 8!, Nlssen shi, Tokyo; Shui Sato, Hachioji-shi, Tokyo; Eiichi Sakamoto, Hanno-shi, v [57] ABSTRACT Saitama-ken; Hiroshi Yamada; Shoji A new polymer compound having the Kikuchi, both of l-lachiojihi, guanidyketimine structural unit of the formula Tokyo, all of Japan [7 3] Assignee: Konishiroku Photo Industry Co., L l

Ltd., Tokyo, Japan 2 CH: [22] Filed: March 19, 1971 2 =NNH iNHZ-(HX)D 1211 Appl. No.: 126,327 NH [30] Foreign Application Priority Data wherein X is an acid radical and n is l or 2 has been synthesized. The said compound is useful as a mordant March 20, 1970 Japan ..45/23l42 in a light sensitive silver halide photographic material in order to prevent undesired migration of an acidic [52] US. Cl. ..96/84 A, 96/57 dye contained in a certain layer f the Said photo- C]. v -.G03c graphi materiaL greatly enhances harpness to Fla! 0 Search A, the image obtained from the aid photographic material. [56] References Cited 3 Claims, No Drawings UNITED STATES PATENTS W 2,882,156 4/1959 Minsk ..96/84 A This invention relates to a light-sensitive silver halide photographic material incorporated-with a novel mordant to improve the sharpness of the resulting image.

It has heretofore been well known that inorder to prevent the irradiation or halation of light in a lightsensitive material thereby improving the sharpness of the resulting image, there is provided in the light-sensitive material a layer containing a material capable of absorbing the said surplus light. For example, there have been proposed such procedures that an anti-halation layer is provided on the back-side of the support, an anti-halation layer is provided between the support and the light-sensitive photographic layer, or an anti-irradiation dye is incorporated directly into the light-sensitive photographic layer. Generally, the anti-irradiation or anti-halation layer contains such a light absorber as dye, colloidal silver, colloidal manganese or carbon black. However, the above-mentioned light absorber has influence on photographic emulsion and brings about various drawbacks such as desensitization, increase of fog, etc., when incorporated into a lightsensitive photographic layer or a layer adjacent thereto, though no substantial problem arises when applied to the back-side of support. Accordingly, in case an anti-halation layer containing a dye is provided adjacent to the light-sensitive photographic layer, the dye diffuses into the light-sensitive photographic layer and absorbs even necessary light to desensitizc the photographic layer. Even when a layer containing such a light absorber as colloidal silver or the like is provided adjacent to the photographic emulsion layer, increase of fog, desensitization and the like drawbacks are brought about in the photographic emulsion layer. Accordingly, the light absorber is incorporated into the light-sensitive photographic layer or a layer adjacent thereto only when sharpness is required at the sacrifice of speed, like in the case of, for example, a high resolution lifhtsensitive photographic material.

In order to overcome the above-mentioned draw backs to effectively improve the sharpness of the resulting image, there has recently been proposed a process using a mordant, which itself is non-diffusing and which has such properties that it captures a dye temporarily or permanently to inhibit the imigration thereof. When such mordant is incorporated together with a dye into, for example, a layer adjacent to the light-sensitive photographic layer, the diffusion of the dye into the light-sensitive photographic layer is controlled to prevent the deterioration of photographic properties. Further, during the step of development, there occur one or more of such phenomena that the captured dye is decolored, the mordant liberates the dye into the treating solution, or the mordant flows into the treating solution without liberation of the captured dye, whereby the adverse effects of the dye on the image after completion can be overcome.

Thus, the use of the mordant results in such advantages that a non-diffusing dye layer can be freely provided in portions where no dye has been able to be used hitherto, and, particularly, an anti-halation layer can be provided in any layer of a multi-layered lightsensitive material. Further, the mordant is not only used for the prevention of halation and irradiation but also applicable to such layer as a filter layer and can be used as a carrier for a filter dye. In view of such uses as mentioned above, the mordant should have an excellent dye-retaining property and should have no detrimental effect on photographic emulsion.

As mordant of this kind, there have heretofore been known dialkylamines disclosed in US. Pat. No. 2,326,057 and urea-polyethyleneimine reaction products disclosed in West German Pat. No. 1,095,120. These mordants, however, are not sufficient in dye-retaining property, so that when said mordants are incorporated into layers adjacent to light-sensitive photographic layers, considerable amounts of the dyes supported by the mordants diffuse and migrate into the photographic layers to deteriorate the photographic properties thereof. Further, the said mordants are required to be used in large amounts, so that there are brought about deterioration in photographic properties of photographic layers due to the mordants themselves and deterioration in physical properties and coatability of the resulting light-sensitive films. Thus, there have not yet been obtained mordants capable of satisfying various conditions required for mordants.

As the result of extensive studies, we have found'that polymers having the guanidylketimine structure shown below are excellent mordants.

Ha NH In the above, the molar content of N-(l,l-dimethyl- 3-oxobutyl)acrylamide in the starting polymers containing the N-(l,1-dimethyl-3-oxobutyl)acrylamide is desirably at least 30 mole percent, and the molar content of monomer unit having the guanidylketimine structure in the polymers containing the guanidylketimine structure which are obtained by condensation of the aforesaid polymers with aminoguanidine or salts thereof is desirably at least 10 mole percent.

Further, the N-(1,1-dim ethyl-3-oxobutyl)acrylamide is highly copolymerizable with other vinyl monomers to give optional copolymers. The said other vinyl monomers include acrylic acid esters, methacrylic acid esters, acrylamides and derivatives thereof, styrene, vinylpyrrolidone, 2-alkylvinylimid'azole derivatives, and vinyl esters such as, for example, vinyl acetate, vinyl butyrate, vinyl propionate and acrylonitrile. However, monomers containing COl-l and SO,H groups, such as acrylic, methacrylic and methylenesulfonic acids are undesirable for the purpose of the present invention and disturb the dye-retaining property. The molecular weights of the polymers having the aforesaid guanidylketimine structure which are used in the present invention are preferably'about 8,500 to 80,000 in view of the compatibility thereof with gelatine, polyvinyl alcohol and the like hydrophilic'colloid layers to which the polymers are applied.

Typical examples of the polymers having the aforesaid guanidylketimine structure are .set forth below together-with synthesis examples thereof, but polymers usable in the present invention are-not limited thereto.

j SYNTHESIS EXAMPLEl To a solution of 30 g. of N-(1,1-dimethyl-3-oxobutyl)ac rylamide in 300 ml. of isopropan'ol was added 0.3 g. of azobisisobutyronitrile, and the resulting mixture was stirred at 70 C. for 8 hours in a nitrogen atmosphere. Subsequently, the mixture was gradually poured with stirring into running water to precipitate 13.3 g. of white powdery poly-N-(1,1-dimethyl-3-oxobutyl)acrylamide, molecular weight 9,550 as measured in 1,4-dioxane (osmotic pressure method), intrinsic viscosity (1 0.030 in 1,4-dioxane at 30C.

Elementary analysis:

Calculated (percent) C 62.22 H 8.99 N 8.05 (11,0

Found (percent) C 62.18 H 9.02 N 7.90

9.16 Grams of the above-mentioned .polymer was dissolved in 60 ml. of 1,4-dioxane. To the resulting solution were added 9.04 g. of aminoguanidine bicarbonate and ml. of glacial acetic acid, and the resulting mixture was reacted with stirring at 50 to 55 C. for 2 hours. Subsequently, the mixture was charged with 55 ml. of pure water, 2 g. of zinc powder and 6 ml. of

glacial acetic acid, stirred for 20 minutes and then suction-filtered. The filtrate dope was poured into 200 ml. of a 10 percent aqueous caustic soda solution to precipitate a resinous product. After allowing the reaction mixture to stand overnight, the resinous product was recovered by decantation, washed 2 or more times with 100 ml. of a 40 percent aqueous caustic soda solution, poured into a mixture comprising 100 ml. of pure water and ml. of glacial acetic acid, filtered and then added to a mixture comprising lliter of acetone and 10 ml. of aqueous sodium chloride. The precipitated resin was recovered by filtration, dissolved in 200 ml. of ethyl alcohol, filtered and then precipitated in 800 ml. of ether. Thereafter, the resin was recovered by filtration, washed with ether and then dried to obtain 7.6 g. of a pale yellowish brown resin, N content 16.79 percent.

svurrrasis EXAMPLE 2 To a solution of N-(1,1-dimethy1-3oxobutyl)acrylamide in 500 g. of carbon tetrachloride was added 0.5 g.

of azobisisobutyronitrile, and the resulting mixture was refluxed for 6 hours in a nitrogen atmosphere. After cooling, the mixture was poured into 3 liters of naphtha to precipitate 50.5 g. of a' resin, molecular weight 20,800, intrinsic viscosity (1 0.085 in 1,4-dioxane at 30C.

Elementary analysis: Calculated (percent) Found (percent) C 61.90 H 8.87 N 7.72

9.16. Grams of the above-mentioned polymer was dissolved in ml. of 1,4-dioxane. To the resulting solution were added 18 g. of aminoguanidine bicarbonate and 25 ml. of glacial acetic acid, and the resulting mixture was subjected to the same reaction and after-treatment as in Synthesis Example 1 to obtain 12.1 g. of a yellowish resin, N content 18.65 percent.

SYNTHESIS EXAMPLE 3 To a' solution of 23.6 g. of N-(1,1-dimethyl-3-oxobutyl)acrylamide and 8.16 g. of 2-ethyl-4-methyl-1 vinylimidazole-in 400 ml. of tert-butanol was added in a nitrogen atmosphere 0.4 g. of azobisisobutyronitrile, and the resulting mixture was stirred at C. for 8 hours. After coolong, the mixture was poured into running water to precipitate 22.19 g. of a polymer, N content 11.29 percent.

9.35 Grams of the above-mentioned polymer was dissolved in ml. of 1,4-dioxane. To the resulting solution were added 6.4 g. of aminoguanidine bicarbonate and 15 ml. of glacial acetic acid, and the resulting mixture was reacted at 50 to 55 C. for 2 hours. Thereafter, the same after-treatment as in Synthesis Example 1 was effected to obtain 10.8 g. of a pale yellowish brown resin, N content 19.32 percent.

SYNTHESIS EXAMPLE 4 To a mixture comprising-35.4 g. ofN- (1,1-dymethyl- 3-oxobutyl)acrylamide, 7.8 g. of vinyl acetate monomer and. 200 ml. of carbon tetrachloride was added in a nitrogen atmosphere 0.4 g. of a,a'-azobisisobutyronitrile, and the mixture wasrefiuxed for 7 hours. After cooling, the mixture was poured into 3 liters of naphtha to deposit a precipitate, which was then recovered by filtration, washed with 200 ml. of naphtha and dried to obtain 36g. of a white polymer, N content 7.51 percent.

15.3 Grams of this polymer was dissolved in m1. of 1,4-dioxane. To the resulting solution were added 14 g. of aminoguanidine bicarbonate and 25 ml. of glacial acetic acid, and the resulting mixture was reacted at 50 to 55 C. for 2 hours. Subsequently, the mixture was charged with 55 ml. of pure water, 2 g. of zinc powder and 6 cc. of glacial acetic acid, stirred for 20 minutes and then suction-filtered. The filtrate dope was poured into 200 ml. of a 10 percent aqueous caustic soda solution to precipitate a resin. After allowing the reaction mixture to stand overnight, the resin was recovered by filtration, washed 2 or more times with 100 cc. of a 40 percent aqueous caustic soda solution and then dissolved in 100 ml. of a 10 percent dilute aqueous hydrochloric acid solution. The resulting solution was subjected to filtration, and the filtrate was poured into a mixture comprising 1 liter of acetone and 10 ml. of sodium chloride water to precipitate a resin.

This resin was recovered by filtration, dissolved in l50 ml. of ethyl alcohol, filtered and then precipitated in 1 liter of ether. Subsequently, the resin was recovered by filtration, washed with ether and then dried under reduced pressure to obtain 11.4 g. of a yellowish resin, N content 20.95 percent.

SYNTHESIS EXAMPLE 5 To a mixture comprising 35.4 g. of N-(l,l-dimethyl- 3-oxobutyl)acrylamide, g. of N-vinylpyrrolidone and 200 ml. of carbon tetrachloride was added in a nitrogen atmosphere 0.4 g. of a,a'-azobisisobutyronitrile, and the total mixture was refluxed for 7 hours. After cooling, the mixture was poured into 2.5 liters of ligroin to deposit a precipitate, which was then recovered by filtration, washed with 200 ml. of ligroin and dried to obtain 42 g. of a yellowish polymer, N content 9. l 8 percent.

15.2 Grams of this polymer was dissolved in v120 ml. of 1,4-dioxane. To the resulting solution were added l4 g. of aminoguanidine bicarbonate and 25 ml. of glacial acetic acid, and the resulting mixture was subjected to the same reaction and after-treatment as in Synthesis Example 1 to obtain 19 g. of a yellowish resin, N content 19.1 percent.

SYNTHESIS EXAMPLE 6 To a mixture comprising 60.8 g. of N-(l,l-dimethyl- 3-oxobutyl)acrylamide, 2 g. of acrylonitrile and 400 ml. of isopropyl alcohol was added in a nitrogen atmosphere 0.6 g. of a,a-azobisisobutyronitrile, and the mixture was reacted at 70 C. for 10 hours. After the reaction, hydroquinone was added, and about one half of the solvent was removed by distillation under reduced pressure. Subsequently, the residue was poured into running water to precipitate 59 g. of a polymer, N content 9.14 percent.

15.8 Grams of this polymer was dissolved in 120 ml. of 1,4-dioxane. To the resulting solution were added 14 g. of aminoguanidine bicarbonate and 25 ml. of glacial acetic acid, and the resulting mixture was subjected to the same reaction and after-treatment as in Synthesis Example 1 to obtain 18.4 g. of a yellowish resin, N content 18.52 percent.

The polymer obtained according to any of the abovementioned synthesis examples may be incorporated into a light-sensitive material in such a manner that an aqueous solution, for example, of said polymer is dispersed in a hydrophilic colloid such as gelatine or polyvinyl alcohol, and the resulting dispersion is charged with a suitable dye and then coated on the support, light-sensitive photographic layer or filter layer of the light-sensitive material. Alternatively, the aqueous solution of the polymer may have previously been incorporated into the light-sensitive photographic layer.

In this case, the hydrophilic colloid may have been incorporated with such a vehicle as anionic, cationic or amphoteric surface active agent, and with such ordinary photographic additives as hardener, stabilizer, etc. If necessary, the polymer may be used in combination with a known mordant.

Light-sensitive materials to which the polymer of the present invention is applicable are those containing various silver halides such as silver chloride, silver chlorobromide, silver bromide, silver iodobromide, etc.

which may be black-and-white or color photographic materials. The amount of the polymer to be incorporated into a light-sensitive material varies depending on the kind of the light-sensitive material, the purpose of application and the kind of a layer to which the polymer is applied, but is, in general, 2 to 40 g. per g. of dry gelatin, for example. In this case, the amount of a dye to be supported by said polymer is preferably 1 to 20 g. As the dye to be supported by the polymer, an acid dye having a sulfone or carboxyl group is particularly preferable. Typical examples of such dye are as follows.

The present invention is illustrated in further detail below with reference to examples.

EXAMPLE 1 To 50 ml. of an aqueous solution containing 3 g. of gelatin and 200 mg. of saponin was added 4 ml. of a 5 percent aqueous solution of the polymer obtained in Synthesis Example 1 of the present invention. Further, 5 ml. of an aqueous solution containing 1 percent of the dye (7) was added thereto. The resulting mixed solution was charged with a given amount of a hardener and then adjusted to pH 6.3, and the total amount of the solution was made 100 ml. to prepare a sample (A). In order to ascertain the effect of the polymer, a sample (B) was prepared in the same manner as above, except that the polymer was not used. Further, acontrol sample was prepared in the same manner as above,except that the polymer and the dye'were not used.

The above-mentioned three samples were individually coated on a subbed cellulose triacetate film base to a dry emulsion layer thickness of 1.5 u, and then dried. On each of the thus formed films, -a high speed silver iodobromide emulsion was coated to obtain light-sensitive films. These films were subjected to Sensitometer Model KS -l (manufactured by Konishiroku Photo Industry Co., Ltd.) and exposed to a light of 160 luxes (5,400K) through blue and green filters having transmission maximums of 450 my. and 525 mu, respectively. Thereafter, the exposed samples were developed at 20 C. for 5 minutes with a developer of the following composition: Developer:

Metol (N-methyl-paminophenol sulfate) 3 g. Anhydrous sodium sulfite 50 g. Hydroquinone 6 g. Sodium carbonate (monohydrate) 29.5 g. Potassium bromide l g. Water to make 2 liters TABLE 1 Photographic Photographic speed to speed to Sample blue light green light Fog Sharpness Control 100 100 0.07 (A) 95 82 0.07 Greatly improved (B) 89 42 0.07

As is clear from Table 1, the film sample (A) containing the polymer having the aforesaid guanidylketimine structure was improved in sharpness to the same extent as that of the film sample (B) containing no such polymer, without being increased in fog as compared with the sample (B). According to microscopic observation, it was found that in the case of the film sample (B), the diffusion of dye into the emulsion layer was marked, whereas in the case of the film sample (A), no such diffusion was substantially observed.

Further, a film sample (C) was prepared in the same manner as above, except that the dye (6) was used in place of the dye (7). On the other hand, a film sample (D) was prepared in the same manner as above, except 9 that the polymer was not used. The samples (C) and (D) were also measured in photographic speed and sharpness to obtain the results as set forth in Table 2.

TABLE 2 Photographic Photographic Sample speed to speed to Fog Sharpness I blue light green light Control 100 100 0.06 (C) 93 80 0.06 Greatly improved (D) 85 37 0.06

Thus, the polymer having the aforesaid guanidylketimine structure was excellent in dye-retaining property and had no' such fear as to bring about any increase of fog, desensitization and the like damages in photographic properties.

EXAMPLE 2 T o 50 ml. of an aqueous solution containing 4 g. of gelatin and 200 mg. of saponin were added 10 ml. of a 6 percent aqueous solution of the polymer of Synthesis Example 2 and 10 ml. of each of 1 percent aqueous solutions of the exemplified dyes (2), (6) and (8). The resulting mixed solutions were individually charged with a hardener, and then the total amount thereof was made 100 ml. Each of these solutions was coated as a black anti-halation solution on a transparent film bases to a dry coat thickness of 3 [1,. On each of the thus formed films, a panchromatically sensitized silver chlorobromide emulsion was coated to prepare film samples.

Control film samples were prepared by using dye solutions in the same manner as above, except that the polymer was not used.

These film samples were measured in photographic speed and sharpness of image. As the result, the film samples containing the above-mentioned polymer were improved in sharpness to the same extent as that of the film samples containing no such polymer, with less degradation in photographic speed as compared therewith. During the course of development, the antihalation layers were completely decolored to transparency.

EXAMPLE 3 Between the red-sensitive layer and green-sensitive layer of a light-sensitive color photographic material, there was provided each of the two colored dye layers prepared in the following manner:

To 50 ml. of an aqueous solution containing 3 g. of gelatin and 100 mg. of saponin were individually added (e) 5 ml. of a 6 percent aqueous solution of the polymer of Synthesis Example 4 and 10 ml. of a l percent aqueous solution of the exemplified dye (7), and (f) 5 ml. of a 6 percent aqueous solution of the polymer 1,0. of Synthesis Example 6 and 10 ml. of a 1 percent aqueous solution of the exemplified dye (7). Thereafter, the

total amount of each of the mixed solutions wasmade' This dye layer not only had no detrimental effect on the red-light sensitivity of the lower red-sensitive emulsion layer but also showed such effect as to cut unnecessary green-light sensitivity to improve and enhance the color sensitivity of the emulsion layer. To the upper green-sensitive emulsion layer, the non-diffusing dye layer showed such effect that it successfully prevented harmful halation to greatly improve the sharpness of the resulting image.

On the other hand, in the case of a light-sensitive material having a dye'layer prepared in the same manner as above, except that the polymer was not used, the dye' diffused and migrated into'the upper green-sensitive emulsion layer and absorbed greenlight', with'the result that the green-light sensitivity was greatly. decreased.

EXAMPLE 4 Red-sensitive and green-sensitive emulsions containing a coupler were coated on a base. On the resulting layer, there was formed a yellow filter layer by coating thereon a-solution prepared by adding 10 ml. of a 6 percent aqueous solution of the polymer of Synthesis Example 5 and 20 ml. of a 1 percent aqueous solution of the exemplified dye (3) to 60 ml. of an aqueous solution containing 3 g. of gelatin and 200 mg. of saponin. Subsequently, a blue-sensitive emulsion containing a coupler was further coated on the yellow filter layer to obtain a light-sensitive color photographic material. The thus obtained color photographic material was subjected to color development and investigated in photographic speed of the blue-sensitive emulsion. As the result, there was observed no desensitization due to diffusion of the dye, and the filter layer showed such filter characteristic as to successfully cut unnecessary blue light sensitivity of the lower layer. From this also, it is understood that the above-mentioned polymer has firmly bonded even to such a dye as the dye (3), which has only one acid radical. During the course of development, the filter layer was decolored to transparency.

What we claim is:

l. A light-sensitive silver halide photographic material comprising one or more layers containing an acidic dye and as a mordant a polymer having structural units of the formula wherein X is an acid radical and n is l or 2.

2. A light-sensitive silver halide photographic materialas in claim 1 wherein the dye and mordant are incorporated into an anti-irradiation or anti-halation layer.

3. A light-sensitive silver halide photographic material as in claim 1 wherein the polymer has a molecular weight of about 8,500 to 80,000.

c reer- 

2. A light-sensitive silver halide photographic material as in claim 1 wherein the dye and mordant are incorporated Into an anti-irradiation or anti-halation layer.
 3. A light-sensitive silver halide photographic material as in claim 1 wherein the polymer has a molecular weight of about 8,500 to 80,000. 